Compounded oil



Patented Apr. 11,1944

COMPOUNDED OIL George H. Denison, Jrl, and Paul C. Condit,

Berkeley, Calif., assignors to Standard Oil Company of C alifornia, SanFrancisco, (Jalif.I a corporation of Delaware No Drawing. ApplicationFebruary 23, 1942. Serial No. 432,040

14 Claims.

This invention relates to new and useful compositions of mattercomprising a hydrocarbon oil containing a new combination of stabilizingagents. This combination comprises a thioether or seleno ether and anoxide, sulfide or selenide having directly connected to an oxygen,sulfur or selenium atom thereof both a metal in a basic form and anacid-forming element such as those occurring in groups Ill-A, IV, VB andVI-B of Mendelyeevs Periodic Table of the Elements. More particularly,the invention involves compounded lubricants containing an anti-oxidantof the type represented by dialkyl thioethers or dialkyl seleno ethersand a stabilizer or activator of the type illustrated by the metal saltsof organo-inorganlc acids, such as acids of the weak acid-formingelements, boron, silicon and arsenic, or organo substituted carbonic andcarbamic acids, or organo-inorganic acids of strong acid-formingelements, sulfur and phosphorus.

The present invention involves the discovery that dispersion inhydrocarbon oils of oxides, sulfides or selenides containing as apreferred group- (A) (X) (Z) (X1) (Rm) in which A represents a basicsalt-forming element or radical, X and X1 are selected from the groupconsisting of oxygen, sulfur or selenium, Z is an acid-forming elementselected from groups III-A, IV, VB and VI-B of Mendelyeevs PeriodicTable, R is an organic radical attached to Z either directly orindirectly through an intervening atom, and n is a whole number no lessthan 1; together with thioethers. seleno others or telluro ethers',imparts new, unpredictable and desirable properties to the composition.

These new properties render the compounded oil particularly useful forvarious purposes. Increased resistance to deterioration under oxidizingconditions comprises one of the principal advantages of the compoundedoils of this invention. This increased resistance is brought about incertain instances by a cooperative action between the two types ofingredients. The thioether, seleno ether or telluro ether type ofcomponent inhibits that kind of deterioration which results in increasedcorrosivity of the oil toward certain bearing metals, such ascadmium-silver or copper-lead bearing alloys. These components alsoinhibit oxidation of the base oil. This antioxidant action is frequentlyenhanced by the metal salts of organo-inorganic acids, this lattercomponent serving to activate the ether compounds.

It is to be understood that the invention is not limited to theforegoing functional features. Different compounds of the general typeherein involved vary in their degree of eifectiveness and may impart oneor more desirable properties to the composition. For example, the amountof wear produced in lubrication of metal surfaces may be reduced ascompared with wear resulting with a straight uncompounded lubricatingoil. In general, however, it has been discovered that the newcompositions herein disclosed are more stable to deterioration by heatand oxidation than is a hydrocarbon oil with which the compositions arecompounded. The new compounding agents of this invention are thereforeuseful where a stabilized oil is desired and resistance to deteriorationis important. An example of such utility is their use as lubricatingoils, particularly in internal combustion engines, to inhibit gumming ofpistons, sticking of piston rings, sludge formation in the crankcase,and the like. The compositions are also useful as heat transfer fluidswhere it may be desirable to inhibit or prevent the formation of adeposit on the metal surfaces from or to which heat is bein conveyed.Likewise, the increased resistance to oxidation imparted to the oils bythe compounds of this invention finds various applications ininsulating. switch or transformer oils.

The salt-like compounds of the type here involved may be regarded assalts of organic substituted acids of boron, silicon, arsenic, sulfur,phosphorus, etc. Metals preferred as the basic component of the saltsutilized in this invention arecalcium,strontium,bariurn,mangnesium,zinc, cadmium, aluminum, zirconium, chromium and molybdenum. Salts ofbismuth. tin, lead, iron, cobalt. nickel, manganese, vanadium, sodium,potassium, copper and silver comprise additional examples of metalsfalling within the broader aspects of the invention. Basic salt-formingradicals such as the ammonium and amine radicals are not precluded.

These compounds may be most conveniently classified as salts of parentacids of the type formulae given hereinafter, even though the compoundsare not in fact, in many instances, formed directly by neutralization ofthe parent acid.

Accordingly, the compounding agents are re- B B u-a R. ii onDlthio-diestar of arsenic acid 8 R A1 R g S H Monothlo-diestat ofmoncthlol-arsenic acid 0R A4018: g OH Monoester of monothion-arsenlcacid 0 B. 440 R POE Diester o! monothlon-araenlc acid Monothlo-dlesterof thion-monothlol-arsanlc acid Monothio-aater thiol of carbonic acidPartial ester 01' tritblo-carbonlc acid B.Orthocarbo nic acid Monoeaiar0t orthocarbonic acid Dicstor oi orthocarbonic acid Trlestar oforthocarbonlc acid and corresponding sulfur derivatives such as- TYPE3.CARBONIC Acms Comamma 1m Oacamc SUBSTITUEN'I A.-Metacarbonic acidPartial ester of carbonic acid R-O-O-OH Partial ester of thion-carbonicacid R-S-{C-OH Monothio-eater oi thion-carbonlc acid B-O-fi-fi HMonoester thioi-thion of carbonic acid TYPE 4.-Ac1ns or Smcon Counmmo mOxoamc suns-nmme A.-Mono-oraano acids of silicon Pentaorthosiiicic acid,HmSisOm Monometasilicic acid, H2810: Dimctasilicic acid, (Hisizos)Trimetasilicic acid, (HcSiaOo) Tetrametasilicic acid, (HaSLiOm)Pentametasilicic acid, (HmSisOxa) Dimesosilicic acid, HzSizOsTrimesosiiicic acid, HoSiaOa Tetramesosilicic acid, HaSioOnPentamesosilicic acid, HaSisOn Triparasilicic acid, Hzsiso'zTetraparasilicic acid, H4Si401n Pentaparasilicic acid, HeSicOnTetratetrerosilicic acid, 11251409 Pentatetrerosilicic acid, H4Si5012 $5Pentercsilicic acid, H2S150n TYPE 5.-ACIDS OF PHOSPHORUS CONTAINING ANORGANIC SUBSTITUENT A.-Acids of trivalent phosphorus l W RO- P-OHMonocstcr oi phosphorous acid R-O-P-OH Dicstcr of phosphorous acidR-P-QH Phosphonous acid B-P-OH Monocster oi phosphonous acid 10 P-OHPhosphinous acid 7' Monothio-phosphonoub acid 8 B B- P Monothio-ester oiphosphonous acid Monoecter o! thiol-phosphonoua acid Dithio-phosphonousacid Diectcr oi dithio-phoophorious m \PBH Thio-phosphonous acidB.-Acids of pentovalent phosphorus (prelei'red) Monocstcx of phosphoricacid Dlestcr of phosphoric acid o Ri -0n Phosphonic acid Monoestcr ofphosphonic acid Phosphinic acid 5 R O.=POH OH Monothio-ester ofphosphoric acid Dithio-cstcr of phosphoric acid Monoestcr oitetrathio-phosphodo acid Dlestcr oi monothlo'phcsphoricacld 1 o==1 1avvMonothio-cstcr of pholphonio we on P43! Monooster oi dithio-phospbonlcacid SH Monothio-estor of tritliio phosphoniciacid s TYPE 6.Acrns orScam Com-Ammo an Monoester of suliiuous acid savor:

Sulilnic acid R OR" S B OH Monoestcr 0t suliinic acid R-Q-OH sulionicacid 0 R0- OH Mouoeltet o! sulfuric acid In all of the foregoing typeformulae R, R

and R" are radicals of hydrocarbon structure.

8 groups containing polar radicals such as 0H, SH.

Cl, NH: and COOH. Likewise, this term includes a radicals containingether, sulfide and ester groups. Thus, throughout the specification andclaims the term "radical of hydrocarbon struc- 10 ture includes:

(a) Aikyl radicals, such as amyl, isoamyl, hexyl, heptyl, octyl, theisomeric octyls, lauryl, dodecyl (normal or branched chain), tetradeeyland cetyl (normal or branched chain) radicals:

II (b) Aryl, such as, the phenyl, diphenyl and naphthyl, radicals; v

(0) Aralkyl, such as phenyloctadecyl and simi- 1 lar alkyl radicalsconnected to the central acidiorming atom, e. g. boron or arsenic, andhaving 20 an aryl groupas asubstituent inthe alkyl chain:

(dl Alkaryl, such as methylphenyl, cetyiphenyl, and other radicals wherethe aryl group 1 I is directly attachedto the central acid-formingclohexyl or other alicyclic radicals;

(I) Oxy radicals such asthma in which the I hydrogen or, anhydroxylgroup has been replaced Q by esteriflcation, etheriflcation,neutralization with a metal, or the like;

-(g) Radicals containing thio, amino, halogen or other groups.

It should be home in mind that in. the fore- SI going type formulae allor the acids listed ma not exist as such and that it is the salt-likederive tlves thereof with which the present invention is concerned.Accordingly, existence of the free acid in a stableiorm is not aprerequisite to the a preparation of the derivatives thereofcontemplatedherein. It should also be observed that various of thesalt-like derivatives are relatively insoluble in organic solvents suchas hydrocarbon oils. However, oil-solubility is not an absoluteprerequisite for utility or the present invention in its broadestaspects, as will be explained in more detail hereinafter; nevertheless,oil-soluble compounds are preferred.

In general, salts and preferably polyvalent metal salts falling withinthe broader aspects of the invention are of: organic substitutedderivatives of acids of boron, organic substituted derivatives of acidsof arsenic, organic substituted carbonic acids, organic substitutedcarbamic acids, u organic substituted acids of silicon, organicsubstituted acids of germanium, such as tri-substituted germanols,germanonic acids, and germanic acid anhydrides, organic substitutedacids of tin such as organo stannonic acids and organo thiol0 stannicacids, organic substituted acids of antimony such as organo stiblnousacids, organo stibonic acids and organo stibinic acids, analogous weakacids of bismuth, chromium, molybdenum and manganese in those instanceswhere organo salt-forming acids are obtainable, and organo substitutedacids of phosphorus and of sulfur.

To illustrate the properties and general methods of preparationapplicable to the foregoing general groups or compounds the followingdis- 1o cussion is given:

TYPE 1.-Acn s or Boson Conranmm an Oacmc m u IMAII'DMITAL SALTS 1mm 7The preferred acids of boron are substituted acids or trivalent boron,and the preferred salts comprise the magnesium, aluminum, calcium,barium, tin and chromium salts of these acids. Examples of such saltsare: the magnesium, aluminum, calcium, barium, tin and chromium salts ofmonododecyl, monotetradecyl, monocetyl, mono-octadecyl,mono-(amylphenyl) mono-(decylphenyl) mono- (dodecylphenyl) mono-(tetradecylphenyl), mono-(cetylphenyl) and mononaphthenyl, boric acids;the magnesium, aluminum, calcium, barium, tin and chromium salts ofdihexyl, dioctyl, didecyl, didodecyl, ditetradecyl, dicetyl,dioctadecyl, diphenyl, dibenzyl, di- (ethylphenyl) di-(amylphenyl) di-(decylphenyl), di-(dodecylphenyl), di-(cetylphenyl), and dicyclohexyl,boric acids; the magnesium, aluminum, calcium, barium, tin and chromiumsalts of dodecyl, tetradecyl, cetyl, octadecyl, amylphenyl, decylphenyl,dodecylphenyl, tetradecylphenyl, cetylphenyl, and naphthenyl, boronicacids; the magnesium, aluminum, calcium, barium, tin and chromium saltsof dihexyl, dioctyl, didecyl, didodecyl, ditetradecyl, dicetyl,dioctadecyl, diphenyl, dibenzyl, di-(ethylphenyl), di- (amylphenyl),di-(decylphenyl), di-(d o d e c y lphenyl) and di-(cetylphenyl) borinicacids.

The substituted acids of boron utilized in the preparation of the saltsof this invention may be obtained by known methods. For example, themonoesters of boric acid and diesters of boric acid are obtainable byhydrolysis of the triester, and the desired salts may be prepared fromeither the unneutralized partially hydrolyzed ester or from the sodiumsalt thereof by reaction with the desired metal ion.

The diesters of boronic acids are obtainable, for example, by the slowoxidation of trialkyl borine. Also, the aliphatic and aromatic boronicacids can be prepared readily by the reaction of Grignard reagents uponalkvl esters of boric acid or the etherate of boron trifluoride insteadof an alkyl borate.

In general, it may be explained that boric esters may be prepared by theaction of alcohols on boric anhydride under pressure. These esters reactwith Grignards reagents to form the boronic acids according to theequation:

When magnesium phenyl bromide is utilized, a methylating action occursso that, in addition to phenyl boronic acid, toluene is obtained. Thelower boronic acid esters are readily hydrolyzed by cold water to yieldthe free boronic acid.

The following will illustrate in more detail a method of preparing atypical substituted acid of boron. Alkyl boronic acids in general may beprepared by this procedure without essential modification:

A l-liter 3-necked flask is fitted with an eiiicient mercury sealedstirrer and one neck provided with a low temperature thermometer and aglass tube for the introduction of nitrogen. The remaining neck carriesa 500 cc. separatory funnel and an outlet tube for nitrogen or otherinert gas. The nitrogen outlet tube and the top of the separatory funnelare connected to two arms of a Y=tube, the third arm of which is sealedby a mercury valve. Dry nitrogen, purified over suliuric acid andalkaline pyrogallol, is allowed to flow through the apparatus for abouttwenty minutes. Then 55 grams (0.53 mol) of pure methyl borate is addedquickly through the sepatory tunnel and washed through with 150 cc. ofanhydrous ether. The flask is suspended in a Dewar dish containing amixture of acetone and solid carbon dioxide and the solution stirredduring cooling. When the internal temperature has fallen to about 75,300 cc. (-9.5 mol) of alkyl magnesium bromide solution (1.66 N) isintroduced slowly through the separatory tunnel over a period of severalhours. The flow of nitrogen and vigorous stirring are maintained duringthe addition and the temperature held below 70. During the addition avoluminous precipitate separates. When the addition is complete, the,mixture is stirred at --'70 for several hours and allowed to stand inthe cooling bath over night to insure completion of the reaction. Theflask is then opened momentarily and the cake 0! precipitate broken intosmall amounts. The apparatus is reassembled and 300 cc. of watercontaining 30 cc. oi sulfuric acid added with stirring and cooling. Theethereal layer is separated and the aqueous layer extracted with 50 cc.of ether. The extract is combined with the main ether layer. Theethereal solution is concentrated on a steam bath and distillationcontinued until all material volatile at the temperature of the bath isremoved. The acid which separates upon cooling the residual liquid isfiltered with suction and may be dried in a nitrogen-filled desiccatorover 65% sulfuric acid. This crude acid may be purified by warming with275 cc. of toluene, the solution filtered at 60 C. and chilledthoroughly to cause crystallization.

The necessity for maintaining extremely low temperatures, as in theabove method, may be avoided by using a less volatile ester as astarting material, for example, by using n-butyl borate.

Example 1.-n-Tetradecanol is converted to the bromide (B. P. 132-135 F.at 2 mm). The Grignard reagent from this bromide is added to n-butylborate and gives a crude impure acid conta-minated-Withthe hydrocarbonCzaHsa. The latter may be removed by dissolving the crude acid inalcohol and chilling. The purified n-tetradecane boronic acid isobtained by evaporation of the alcohol'and crystallization frompetroleum ether.

Example 2.Cetyl alcohol is converted to the bromide. The Grignardreagent from this bromide is added to a suitable borate ester such asthe n-butyl borate.

Example 3.Pheny1 magnesium bromide is added to n-butyl borate to obtainthe benzene boronic acid as in the foregoing examples.

Example 4.Cetylphenyl magnesium bromide obtained from cetyl benzene maybe used to prepare cetylphenyl or cetyl benzene boronic acid.

As previously indicated, salts of the foregoing acids may be prepared bytreating the acid with aqueous alcoholic sodium hydroxide and thenprecipitating the various salts by adding an aqueous solution containingthe desired metal ion. For example, cetyl boronic acid is reacted withaqueous alcoholic sodium hydroxide to give sodium cetyl boronate fromwhich various salts are prepared as follows:

Example 5.Aqueous calcium chloride is added to the aqueous alcoholicsolution of sodium cetyl boronate to precipitate calcium cetyl boronate.The precipitate is filtered, washed and dried, or it may be taken upimmediately upon precipitation by dissolving in an organic solvent suchas a hydrocarbon mineral oil.

Example 6.--To prepare the zinc salt, aqueous zinc chloride solution isadded to the alcoholic sodium cetyl boronate solution.

Example 7.-To prepare the magnesium salt, aqueous magnesium chloride ormagnesium sullate solution is added to the alcoholic sodium cetylboronate solution.

Example 8.To prepare the aluminum salt', aqueous aluminum chloride oraluminum sulfate solution is added to the alcoholic sodium cetylboronate solution.

Example 9.-To prepare the tin salt, aqueous tin chloride solution isadded to the alcoholic sodium cetyl boronate solution.

Example 10,.To prepare the lead salt, aqueous lead acetate solution isadded to the alcoholic sodium cetyl boronate solution.

Example 11.-To prepare the chromium salt, aqueous chromic sulfate orchrome alum solution is added to the alcoholic sodium cetyl boronatesolution. i

Example 12.To prepare the manganese salt, aqueous manganese sulfatesolution is added to the alcoholic sodium cetyl boronatesolution.

Example 13.--To prepare the nickel salt,- aime-v ous nickel chloridesolution is added to .the alcoholic sodium cetyl boronatesolution.

Example 14.-To prepare the cobalt salt, aqueous cobalt chloride solutionis added to the alcoholic sodium cetyl boronate solution.

A borinic acid is obtained when boron diphenyl chloride or bromide istreated with sodium hy droxide and the clear solution neutralized-withhydrochloric acid. The dibenzene borinic-acid results and readily formsalkali metal salts which in turn may. be converted to a polyvalentmetalsalt by reaction with the desired metal ion.

Salts of the partially esterified boric acids may be prepared bypartially hydrolyzing the ester with sodium hydroxide to obtain thesodium salt of the partial ester. Other salts may be precipitated bydouble decomposition in accordance with the methods described in theforegoing examples.

TYPE 2.-Acms or Ansemc CoN'rAmnm AN Ox- GANIC SUBSTITUENT AND METALSALTS Tnnanor Aryl arsine oxides may be regarded as the anhydride ofarsonous acids. 'Arsonous acids are also called dihydroxy arsines. Theunsubstituted oxides are readily obtained by treating the correspondingdlhalogenated arsines with alkali hydroxides or carbonates in thereaction- They form white crystalline substances readily soluble inorganic solvents, sparingly in alcohol, and insoluble in water. Thearsine oxides are amphoterio, dissolving in concentrated aqueous causticalkalies, and will form the disodium salt when such solutions areproperly treated.

Although unsubstituted aryl dihydroxy arsines or arsonous acidscorresponding to the formula- RAS(OH) 2 have not been isolated, theesters may be successfully obtained; for example, by the interaction ofphenyl dichloro arsine and sodium alcohoiates or phenylates- In the caseof the catechyl ester the lead salt of catechol is employed. Theseesters may be converted to the metal salt of the half ester or bothhydrocarbon radicals of the ester group substituted with metal to obtainthe compounding agents of this invention. More detailed descriptions oi!methods of preparing various salts will be given hereinafter.

Several methods are available for the preparation of aliphatic arsenicacids: (1) Hydrolysis of the corresponding alkyl arsine oxyhalides ortetrahalides- (2) Oxidation of primary aliphatic dihalogenated arsinesby means of moist silver oxide or hydrogen peroxide-- (3) Oxidation ofalkyl arslnes by atmospheric oxygenthe arsonic acids according to thereac- 7 These sodium salts may be converted to other metal salts bydouble decomposition, e. g., the calcium salts are precipitated byadding aqueous calcium chloride to aqueous solutions of the sodiumsalts. Dlalkyl arsinic acids may be prepared from secondary trivalentaliphatic arsenicals by oxidation with oxygen or mercuric oxide; fromalkyl dichloro arsines and bromine in the presence of water, or by theaction of mercuric oxide upon alkyl arsine oxides. The lower mem-. bars01 this series of acids are highly stable and readily form metallicsalts.

Thio-dialkyl arsinic acid salts are obtained by the action of hydrogensulfide upon the respective metal dialkyl arsinates or from the dialkylarsinic disulfides and metallic salts in alcoholic medium. Theefiectiveness of some of these thio-dialkyl arsinates may not be dueprimarily to the compounds themselves but rather to decompositionproducts thereof after addition to oil, as contemplated by the presentinvention.

An additional example of the preparation of thio compounds utilizes thearyl arsine sulfides and sesquisulfides as starting materials. Thearsine sulfides maybe obtained by the action of hyidirogen sulfide uponthe corresponding arsonic ac s:-

These compounds form sulfa-salts with either alkali olysulfides oralkali sulfides and sulfur:

R-AsS+M:S-l-S RASS(SM) z where Mis an alkali metal. The aryl arsinesesquisulfides also dissolve in alkali polysulfides, formingsuite-salts;

R -AszSa +MaS2+M2S 2RA5S (SM) There are also a number or methods bywhich aryloralkaryl arsenic acids may be prepared.

The following are exemplary:

The reaction with normal diazo compounds is facilitated by the use ofcatalysts, such as metallic copper, cuprous hydroxide or copper salts inthe absence of free alkali;

(2) By oxidizing aryl arsines with nitric acid RAsHz-I-30 RAsO(0H) 2 (3)By oxidizing arslne oxides, e. g., with hydrogen peroxide in alkalinesolution RASO-I-O-E-H2O- RASO (OH) 2 The metal salts are readily formedfrom these acids.

Esters may be prepared from sodium alkoxides and aryl arsineoxychlorides:

CsH5AsOC12+2RONa- CsHsASO (OR) 2+2NaC1 or by double decompositionbetween alkyl iodides and silver arsonates, e. g.:

CsHsASO (OAg) 2+2RI- CsHsAsO (OR) 2+2AgI These esters in turn may bepartially hydrolyzed and the sodium or other metal salts of the halfester obtained.

Hydroxy aryl arsenic acids may be obtained by directly heating phenolarsenates (Bchamp reaction) or from amino arsenic acids by diazotizingand replacing the diazo group with a hydroxyl in the usual manner.

It should be observed that the straight phenyl substituted acids ofarsenic and their salts are, in general, relatively insolubl in organicsolvents such as hydrocarbon oils. Accordingly, it is preferred toutilize an aryl radical containing an alkyl substituent since it isfound that such substituted aryl radicals impart greater oil solubilityto the final compounds. However, it is to be understood that oilsolubility is not an absolute prerequisite for utility of the presentinvention in its broader aspects, as will be explained in more detailhereinafter.

Salts of heterocyclic substituted acids of arsenic are also contemplatedwithin the scope of the invention: thienyl-2-arsonic acid or oil-solublederivatives thereof, and methyl benzodiazole arsenic acids areexemplary.

The preferred acids are substituted acids 01. pentavalent arsenic andthe preferred salts cemprise the oil-soluble magnesium, aluminum,calcium, barium, tin and chromium salts of these acids. Examples ofsalts of organo substituted acids of arsenic are:

Partially esterifled arsonous acids (type formula of salt-forming acid,

The magnesium, aluminum, calcium, barium, tin and chromium salts ofhexyl, octyl, decyl. tetradecyl, cetyl and benzyl, phenylarsonous acids;the magnesium, aluminum, calcium, barium, tin and chromium salts ofcetyl and cetylphenyl, cetylphenylarsonous acids.

Salts of dlallcyl arsinic acids,

The magnesium, aluminum, calcium, barium, tin and chromium salts ofdi-isoamyl, dihexyl, dioctyl, dideoyl, didodecyl, ditetradecyl, anddicetyl, arsinic acids.

Salts of alkaryl arsenic acids, R-ihflOH)! The magnesium, aluminum,calcium, barium, tin and chromium salts of amylphenyl, decylphenyl,dodecylphenyl, tetradecylphenyl and cetylphenyl, arsenic acids.

Salts of aryl arsenic acids,

R-rhsKOH);

The magnesium, aluminum, calcium, barium, tin and chromium salts ofnaphthyl and hydroxyphenyl, arsenic acid.

Salts of partially esterifled aryl arsenic acids (type formula ofsalt-forming acid,

The magnesium, aluminum, calcium, barium, tin and chromium salts ofmonohexyl, monooctyl, monodecyl, monotetradecyl, monocetyl andmonobenzyl, esters of phenylarsonic acid.

Salts of alkyl arsenic acids,

,The magnesium, aluminum, calcium, barium, tin and chromium salts ofdodecyl, tetradecyl, cetyl, octadecyl, n-propyl and allyl, arsenicacids.

Salts of partially esterified alkyl arsenic acids (type formula ofsalt-forming acid,

R-zfiTOR' 0 OH The magnesium, aluminum, calcium, barium, tin andchromium salts of monodecyl, monododecyl, monotetradecyl and monocetyl,esters of propylarsonic acid.

In general, the alkali metal salts are the easiest prepared, and theother desired metal salts utilized in this invention may be obtainedfrom aqueous or aqueous alcoholic solutions of the alkali metal salts byadding an aqueous solution containing the desired metal ion. Forexample, solutions of the sodium salts of arsenic acids may be preparedby neutralization of the free acid.

Example 15.--Aque0us calcium chloride is added to an aqueous solution ofsodium allyl arsonate to precipitate the calcium allyl arsonate. Theprecipitate is filtered, washed and dried or it may be taken upimmediately upon precipitation by dissolving in an organic solvent suchas a hydrocarbon mineral oil.

Example 16.To prepare the zinc salt, aqueous zinc chloride solution isadded to the sodium allyl arsenate solution.

Example 17.To prepare the magnesium salt,

" Example'ZZ-Toprepare theinanganese salt,

- aqueous manganese sulfate solution is added to.lhe'sodinmeEyl"arsonate solution.

E$ample"23. To prepare thenickeisalhng. e-

ous nickel chloride solution is added to the so-:Jmnmsallyl-arsonatesolution.

ous cobalt chloride solution is added to the sodium ally] arsonatesolution.

tsaltssoiiotheriaikyixarsonic acids areQor-epared in a similar manner.'Vifherethe-alirali'metal-salt "of the parent acid is insufiicientlywater-sluble to give a suitable dispersion icomplete watersolubility isunnecessary in many instances), auxiliary solvents may be mixed with thewater to aid solution of the sodium salt. Alcohol is an example of anauxiliary solvent.

Salts of the partially esterified arsonic acids may be prepared bypartially hydrolyzing the ester, e. g. with sodium hydroxide to obtainthe sodium salt of the partial ester. Other salts may be prepared bydouble decomposition in accordance with the methods described in theforegoing examples.

TYPE 3.--CARBONIC Acrns CONTAINING AN ORGANIC SUBSTITUEN'I AND METALSALTS THEREOF The preferred acids are organo substituted acids ofthio-carbonic acids, and the preferred salts comprise the magnesium,aluminum, calcium, barium, tin and chromium salts of these acids.Examples of metal thio-carbonates are:

decyl, monocetyl, mono octadecyl, mono- (amylphenyl) mono- (decylphenyl)mono- (dodecylphenyl) mono- (tetradecylphenyl) mono-(cetylphenyl), andmononaphthenyl, esters of dithiol carbonic acid; the magnesium,aluminum, calcium, barium, tin and chromium salts of monododecyl,monotetradecyl, monocetyl, mono-octadecyl, mono-(amylphenyl), mono-(decylphenyl) mono-(dodecylphenyl) mono-(tetradecylphenyl)mono-(cetylphenyl) and mononaphthenyl, esters of trithio carbonic acid.

Corresponding derivatives of orthocarbonic acid in which sulfur may ormay not be substituted for one or more of the oxygens of the carbonateradical, and of oxy-metacarbonic acid are contemplated within thebroader aspects of the invention. It should be observed that the lowermembers of the oxy-carbonate series, such as salts of methyl or ethylcarbonic acid, tend to be decomposed by water which is a disadvantage. 5Also note that carbonates and carboxylates are distinctly differenttypes of compounds.

The various substituted carbonic acids and salts thereof utilized inthis invention may be obtained by known methods. The primary esters illof carbonic acid are not stable in a free condition but may be preparedfrom the alcohols and carbon dioxide at low temperatures. The bariumsalt of methyl carbonic acid is obtained on conducting carbon dioxideinto a methyl alcohol solution of anhydrous barium hydroxide. Ma

nesium methoxide combines :with carbon dioxide toform magnesium-methyl-carbonate. 'I'hetpo tassium salt oiethyl carbonic acid.separates in pearlyscales onfadding'carbon dioxide tothepoiassiumalcoholataT m magnesium salt oliethyl --carhon:lc acid from theelectrolysis oi a well-cooled sodium- .eihylate. solution when using "umelectrodes and a ihiglh current density. The barium salt oi'ethylcarbonic acid is obtainable by con- -ducting carbon dioxide :into aiyeryconcentrated ealcoholiazsolution-zofhariumcthyiate. -Alum1num Idie'thylate, monoethylcarbonate,

. .HHGCzHsMOCOOGiHs results from the action or carbon dioxide onaluminum triethylate inbenzene solution. The sodium salt of phenyl,carbonic acid may be prepared by the action of dry carbon dioxide on 5perfectly dry sodium phenate.

The salts of esters of organo thio-carbonic acids may be obtained- (1)By the union of the anhydrides, C02, C03,

can, with-- (a) The sulfides of the alkali and alkaline earth metals;(b) The mercaptides of the alkali metals;

and (o) By the union of the last two with alcoholates; (2) By thetransposition of the salts thus obtained with alkyl halides and alkylenedihalides;

(3) By the action of alcohols and alcoholates,

mercaptans and alkali mercaptidea on COClz, CLCOzCzHs, CSClz, andCLCSzCzHs.

Where the pure ester results in these syntheses, partial hydrolysis andneutralization of the free acid group may be utilized to obtain thesalt.

The alkali salts oi. thiolthion carbonic acid esters (sulfothio-carbonicacid esters) are conveniently obtained by the interaction of carbondisulflde and alkali hydroxides in alcoholic solution by reactions, suchas- CS2+KOH+C2H5OH- C2H5OCSSK OCH:

Alkali salts of trithio-carbonic acid are the products of interactionbetween carbon disulflde and alkali sulfide. The alkali salts of thetrithiocarbonic acids may be reacted with ethyl chloride or the like toreplace the alkali metal atom with the corresponding organic group toform the ester.

TYPE 4.Ac1os or SILICON CONTAINING IAN OR- GANIC SUBSTITUENT AND METALSALTS Tmmeor from the bromide by potassium hydroxide solution at 100 C.or by treating the silicone, (CsH5)2SiO, with Grignard reagent.Triphenyl silicol trisulfonic acid, (CsHeSOaH) aSiOH, is made by gentlywarming one part of the above silicol with six parts of fuming sulfuricacid. When it is all dissolved, the solution is poured into cold water,neutralized with barium carbonate, then gently warmed and filtered frombarium sulfate. Evaporation of the filtrate yields the barium salt inwhite flakes.

Triethylsilyl 4 trimethylplumbyl benzene, (C2H5)3SiCsH4Pb(CH3)3, isobtained from the magnesium compound of triethyl p bromophenylmonosilane and trimethyl lead chloride in ether.1-triethylsilyl-4-triethylstannyl-benzene, (CzH5)3SiCsH4Sn(C2H5) 3, issimilarly prepared from the magnesium compound of triethylp-bromophenylmonosilane and triethyl tin bromide.1-triethylsilyl-4-diphenylarsyl-benzene, (C2H5) 3SiC6H4AS(CsH5) 2, isproduced from the sodium compound of diphenylchloro arsine andtriethyl-p-chlorophenyl monosilane in ether and a little acetic ester.

TYPE 5.Acrns or PHOSPHORUS CONTAINING AN Oaoamc Suns-rrrrmrrr AND METALSALTS THERE- The salts of the substituted acids of Phosphorus involvedherein are preferably formed from substituted acids of pentavalentphosphorus. Substituted phosphoric acids containing at least twelvecarbon atoms are preferred, but where the salts are sufliciently solublein oil acids containing fewer carbon atoms may be utilized. Examples ofpreferred type acids are alkyl or alkaryl substituted phosphoric acidshaving at least twelve carbon atoms in the molecule. The pre* ferredacids are monoesters of orthophosphoric acids or mixtures containing themonoester and the preferred salts are illustrated by the magnesium,aluminum, calcium, barium, tin and chromium salts of monododecyl,monotetradecyl. mono-octadecyl, monocetyl, mono-oleyl, mono-(amylphenyl), mono- (decylphenyl) mono- (dodecylphenyl) mono-(tetradecylphenyl) mono- (cetylphenyl), mono (di amylphenyi), andmono-naphthenyl, esters of phosphoric acids.

The substituted acids of phosphorus utilized herein may be prepared bymethods known in the art. For example, a mixture of a higher alcohol andphosphorus pentoxide in ethyl ether may be refluxed for several hours.The reaction by which the substituted phosphoric acid is formed in thisprocess is believed to be represented by the following equationwhere Ris an alkyl radical. The alkyl ethyl phosphoric acid is soluble inether, while the ethyl metaphosphate is not, and the ether solution ofthe former may be separated from the latter by decantation. In preparingthe metal salts herein involved, the ethyl group in the ethyl phosphoricacid above mentioned may be hydrolyzed to form the metal salt of themonoalkyl orthophosphoric acid, i. e. the salt of RHzPOi. This type ofprocess is not limited to the alkyl derivatives but includes aryl ethylphosphoric acid, alkaryl ethyl phosphoric acid, aralkyl ethyl phosphoricacid and ethyl phosphoric acids containing a cyclic non-benzenoid group.

Acids of trivalent phosphorus containing an organic substltuent may beprepared by methods known in the art. For example, the symmetricalesters, P(OR)3, are obtained from phosphorous trichloride and the sodiumalcoholates and are converted by water or dilute acids into the dialkylesters, POH(OR)2, where R is alkyl. Likewise, the symmetrical esters maybe changed to the salt of the monoor di-ester by the action of an alkalihydroxide. The reaction of phosphorous trichloride on the alcoholsyields the dialkyl esters. The symmetrical esters are isomerized byalkyl iodides into the alkyl phosphonic acid esters which in turn can beconverted to salts by hydrolysis and neutralization.

The thioacids of phosphorus may be prepared by various methods. Forexample, a mixture of phosphorus pentasulfide and a higher alcohol, orof a mercaptan and phosphorus pentoxide, or of a mercaptan andphosphorus pentasulfide, or a three-component mixture, such asphosphorous pentoxide, pyrophosphoric acid and a mercaptan, may bedirectly fused and reacted in proportions to give acid esters ofthioacids of phosphorus. The reaction in the three-component mixture isbielieved to be represented by the following equat ons:

The metal salts of the various substituted oxyacids of phosphorus may beconveniently prepared by reacting the acid with sodium hydroxide orpotassium hydroxide and then precipitating the desired metal salt from asolution of the sodium or potassium salt by the addition of theappropriate metal ion. The salt also may be prepared by the directneutralization of the acid as, for example, with lime where the calciumsalt is to be obtained. The calcium salt may also be prepared in anon-aqueous environment by the reaction of calcium carbide with the freesubstituted acid of phosphorus.

The preferred acids are organo acids of pentavalent phosphorus, and thepreferred salts comprise the oil soluble magnesium, aluminum, calcium,barium, tin and chromium salts of these acids. Examples of salts oforgano substituted acids of phosphorus are:

Partially esterified phosphorous acids (type formula of salt-formingacid,

R-O- P-O H) H The magnesium, aluminum, calcium, barium. tin and chromiumsalts of monododecyl, monotetradecyl, monocetyl, mono-octadecyl, mono-(hexylphenyl) monodecylphenyl) mono- (tetradecylphenyl) monocetylphenyl) and mono-(octadecylphenyl), esters of phosphorous acid.

Diesters-(type formula,

The magnesium, aluminum, calcium, barium, tin and chromium salts ofdihexyl, didodecyl, ditetradecyl, dicetyl, dioctadecyl, di-(hexylphenyl) di- (decylphenyl) cli- (tetradecylphenyl) di-(cetylphenyl)and di- (octadecylphenyl), esters of phosphorous acid.

Partially esterifled phosphonous acids (type formula of salt-formingacid,

n-(ig-on) The magnesium, aluminum, calcium, barium, tin and chromiumsalts of hexyl, octyl, decyl, dodecyl, tetradecyl, cetyl, and octadecyl,esters of phenylphosphonous acid; the magneslum, aluminum, calcium,barium, tin and chromium salts of benzyl, ethylphenyl, amylphenyl,decylphenyl, dodecylphenyl, tetradecylphenyl, and cetylphenyl, esters ofphenylphosphonous acid.

Partially esterifled acids of pentavalent phosphorus (type formula ofsalt-forming acid,

The magnesium, aluminum, calcium, barium, tin and chromium salts ofmonododecyl, monotetradecyl, monocetyl, mono-octadecyl, mcno-(hexylphenyl) mono- (decylphenyl) mono- (tetradecylphenyl) mono-(cetylphenyl), and mono-(octadecylphenyl), esters of phosphoric acid.

Diesters-(type formula,

The magnesium, alumina, calcium, barium, tinand chromium salts ofdihexyl, didodecyl, ditetradecyl, dicetyl, dioctadecyl, di-(hexylphenyl)di (decylphenyl, di (tetradecylphenyl), di-(cetylphenyhanddi-(octadecylphenyl) esters of phosphoric acid.

Partially esterified phosphoric acids (type mula of salt-forming acid,

for-

The magnesium, aluminum, calcium, barium, tin and chromium salts ofhexyl, octyl, decyl, dodecyl, tetradecyl, cetyl, and octadecyl, estersof phenylphosphonic acid; the magnesium, aluminum, calcium, barium, tinand chromium salts of benzyl, ethyiphenyl, amylphenyl, decylphenyl,dodecylphenyl, tetradecylphenyl, and cetylphenyl, esters ofphenylphosphonic acid.

of barium carbonate.

esters are obtainable by the union of alkylenes Partially esterifiedthioacids of pentavalent phosphorus (type formula of salt-forming acid,

The magnesium, aluminum, calcium, barium,

tin and chromium salts or -monododecyl,

monotetradecyl, monocetyl, mono-octadecyl, mono- (hexylphenyl) mono-(decylphenyl) mono- (tetradecylphenyl) mono- (cetylphenyl), andmono-(octadecylphenyl), esters of tetrathiophosphoric acid.

Diesters-(type formula,

The magnesium, aluminum, calcium, barium, tin and chromium salts ordihexyl, didodecyl, ditetradecyl, dicetyl, dioctadecyl, di-(hexylphenyl)di-(decylphenyl) di- (tetradecylphenyl) di-(cetylphenyl) and di-(octadecylphenyl) esters of tetrathiophosphoric acid.

2,252,984 and 2,252,985 issued August 19, 1941.

It is to be understood that any of the salts of the acids of phosphorusdisclosed'in said patents may be utilized in, and are contemplated asfalling within the scope of. this invention insofar as the salts oforgano inorganic acids are concerned.

TYPE 6.-Acms or Scum Conrnnmm 1m Oncmc sunsrn-csm: m Mam. Sums TnmanorThe normal or dialkyl esters of sulfuric acid may be prepared by thereaction of alkyl iodides and silver sulfate or from chlorosulfonicesters or sulfuryl chloride and sodium alcoholate, as well as by othermethods known in the art. These diesters may be hydrolyzed to the acidor monoester of sulfuric acid, which in turn may be converted to saltssuch as involved herein.

The alkyl acid esters of sulfuric acid also may be prepared by reactionof alcohols with concentrated sulfuric acid and boiling the product ofreaction, after dilution with water, with an excess Likewise, the alkylacid with concentrated sulfuric acid.

Alkali metal salts oi. alkyl thiosuliuric acids may be prepared byacting on alkali thiosuliates with primary saturated alkyl iodides orbromides. The free acids are not stable. Likewise, alkyl thiosulfonicacids are only stable as salts or esters. They are formed by the actionof the chlorides of sulfa-acids on potassium sulfide, for example- Alkylsulfinic acids or salts thereof may be formed as follows- (1) By theoxidation of dry sodium mercapitides in air- RSNa-I-OrRSOaNa (2) By theaction of $02 on zinc alkyls or magnesium alkyl halides or by the actionof 802C]: on magnesium alkyl halides- (3) By the action of zinc on thesulfonyl chlorides- Salts of aryl sulfinic acids may be prepared bytreating an aryl sulphon chloride with zinc- 2RSOzCl+2Zn- (RSO2)2Zn+ZnCl2 Salts of aryl thiosulfonic acids may be prepared by treatingsulphon chlorides with metallic sulfides, for example- RSOzCl+KzS-RSO:SK+KC1 MISCELLANEOUS COMPOUNDS Sodium triphenyl germanolate,(CeHsMGeONa, is the oxidation product of sodium triphenyl germanide,(CsHshGeNa, the operation being carried out in the dry state or inbenzene or in liquid ammonia solutions. The product from the lattersolvent contains 1 mol of ammonia of crystallization.

Trimethylstannyl-triphenyl germane,

(CH3) aSn.Ge (CsHs) a is readily obtainable by treating a liquid ammoniasolution of sodium triphenyl germanide with tin trimethyl bromide.

Diphenyl stibinous acid, (CsH5)2SbOOH, may be prepared as follows: Add17 grams Na to a solution of 40 grams SbCls and 40 grams CGHSCI in fourtimes its volume of CsHs to form diphenyl stibine trichloride. Triphenylstibine and triphenyl stibine dichloride are also formed. Thetrichloride can be separated from the triphenyl stibine by extractionwith hot dilute HCl. It is crystallized from the latter. Small amountsof the dichloride as impurity do not matter as they are separated in thenext step. The trichloride is dissolved in alcohol and NH40H is added.This precipitates diphenyl stibinous acid, but not the hydroxide of thedichloride. Salts of this acid may be prepared by known methods.

Bis.(3.5 dichlor--methoxyphenyl) stibinous acid, (CHaOCsHzClzhSbOOI-I,is prepared from tris-(4-methoxyphenyl) stibine by chlorinating asolution of one part of the stibine and fifteen parts of CHCla for sixhours at 0 C. 2.4.6.t1.1- chloranisol is also formed. Crystallize fromCI-IC]: and benzene solution. vHydrolyze by dissolving in ether, addingabsolute alcohol, and then aqueous alcohol solution, and finallyprecipitating with water. The tris-(4-methoxyphenyl) stibine is obtainedby adding sodium to a mixture of SbCl: and 4-bromanisol in benzene.

Benzene stibonic acid, CeH5SbO OH 2t First prepare phenyl antimonydichloride by heating triphenyl stibine with SbCla and xylene at 240-245C. under pressure. Crystallize the reactionproduct from benzene.Saturate an ethereal solution of the'phenyl antimony dichloride in thecold with C12, evaporate the ether,

and dissolve the resulting tetrachloride in dilute NaOH. To obtain theacid, precipitate with dilute HCl.

The barium salt of the above acid may be prepared by adding bariumchloride to an ammoniacal solution of the acid.

Aromatic stibonic acids in general may be prepared by a diazo reactionin which a diazo com.-

pound is treated with antimony oxide in the presence of a polyhydricalcohol such as glycerol or mannitol; e. g. a solution of antimony oxidein HCl, to which glycerine has been added, is poured into an ice-cooledsolution of diazotized aniline and NaOH is then added. The resultingphenyl stibonic acid is precipitated with HCl and may be purified.Similarly, p-tolyl stibonic acid, p-chlorophenyl stibonic acid, andm-chloro-pacetyl aminophenyl stibonic acid may be formed.

Alkyl stannonic acids may be prepared by reacting an alkyl bromide withan alkaline aqueous solution of potassium hydrogen stannite in thepresence of alcohol. Also, by the interaction of SnClz with theappropriate hydrocarbon iodide in alcoholic KOH at low temperatures thefollowing stannonic acids have been prepared: phenyl, benzyl,u-naphthyl, allyl, dichloromethyl, l-bromoethyl, and acetonyl stannonicacids. p-chlorophenyl stannonic acid,

may be prepared by: heating (p-ClCeHO :Hg and This dichloride isconverted to the trichloride. p-ClCeH4SnCla, by heating with SnCl in abomb tube at stannonic acid is prepared by dissolving the resultingtrichloride in petroleum ether and adding an excess of 5% aqueous KOH.

Salts of the foregoing acids may be prepared by neutralization, doubledecomposition and various known methods.

Amine salts of the acids disclosed in this specification fall within thebroader aspects of the invention as heretofore indicated. Examples ofsuitable amines are the alkyl amines, such as triethyl amine; thealkylol amines like triethanol amine; and the aromatic amines, such asaniline. Nitrogen bases obtained from petroleum, and especially reducednitrogen bases such as homologues of piperidine, are also included as anamine with which the salts of this invention may be made.

Reference has previously been made to derivatives of halogenated organoacids of the type herein disclosed. These compounds are usefulparticularly where, in addition to the properties previously disclosedherein, enhanced illm strength. oiliness or reduction of wear isdesired. Examples of halogenated acids, the salts of which may beutilized in accordance with this invention, are 2-chlorophenyl arsonicacid, 4-chlorophenyl arsonic acid, and the half esters of these acids;p-chlorophenyl boronic acid, p-bromophenyl boronic acid, and chlorinatedthio-acids, acids, chlorinated thio-arsonic acids, chlorinatedthio-arsenous acids, chlorinated thio-arsonous acids, and partial estersof these acids. Polyvalent metals salts, such as magnesium, aluminum,calcium, barium, tin and chromium salts of the acids in the foregoinglist, are preferred.

The proportion of the metal salts of organo inorganic acids hereindisclosed which may be added to hydrocarbon oils according to theprinciples of the present invention may vary widely,

depending upon the uses involved and the properties desired. As littleas 0.05 by weight of various of the compounds gives measurableimprovements. From approximately 0.1% to 2% of the compounds may beadded to lubricants where enhanced stability under oxidizing conditionsis desired. More than 2% of the compounds may be utilized for variouspurposes, e. g. for preparing lubricating greases and concentratescapable of dilution with mineral lubricating oils and the like.Concentrates containing high percentages of the addition agents comprisea convenient method of handling the ingredients and may be marketed assuch as addition agents for lubricants in general as well as for otherpurposes.

The compounded hydrocarbon oils herein disclosed may have one or moreadvantages depending upon the particular compounding agents selected,the proportions utilized and the environment or use which the compoundedoil is to encounter. It should be observed, for example, that eventhough a compounded oil may be somewhat corrosive to copper-lead orcadmium-silver bearing metals, Babbitt bearings may be little if at allaffected by such corrosive action. Hence, compounded oils which may notbe particularly desirable for lubrication of copper-lead orcadmium-silver bearings at high temperatures where corrosion becomes afactor of importance may be highly useful and extremely advantageous inconjunction with operations where bearings of babbitt or othercorrosive-resistant bearing metals are utilized. Likewise, compoundedoils in which the addition agent is not sufliciently powerful tostabilize the oil against deterioration by oxidation under the mostsevere conditions may be highly useful in those applications where thetemperatures or oxidizing conditions encountered are not so severe, e.g. in a transformenoil. The present invention in its broader aspects istherefore not limited to the particular ingredients having all or thegreatest number of advantages obtainable, but embraces various ofthe-less advan-' tageous addition agents which'will find utility inparticular applications where all the possible improvements in theproperties may not be required or where the standard of performance maynot be so high.

In the preparation of either the finished oils of the invention or thebases or concentrates referred to, complete or clear and homogeneoussolution is not always necessary. Blending agents such as chlorinatedthio-arsinic' or homogenizers may be employed, if desirable, to preventsedimentation of the less oil-soluble agents but it has been found thatthe possible presence of additional oil-insoluble agents is not in allcases deleterious to the function of the compositions in their intendedmanner.

Even in those cases where suitable oil solu-" bility is not obtainableby blending agents, it will be found that various of the addition agentsof only limited oil-solubility may be utilized. This is particularlytrue in greases where dispersion of the additive in finely powdered formmay be adopted and beneficial functions obtained. In

'most liquid lubricating oils, oil-insolubility of the ment of thecombination is a stabilizer of the type represented by dialkylthioethers and dialkyl selenides. Examples of thioethers operative forthe purpose of the invention are high molecular weight dialkylthioethers containing at least one long carbon chain. By long carbon chais meant a radical containing at least eight to ten carbon atoms. Byhigh molecular weight thioethers it is intended to designate thioetherscontaining in the order. of a total of twelve or more carbon atoms.Examples of seleno ethers are the corresponding high molecular weightdialkyl monoseleno ethers.

Specific high molecular weight dialkyl thioethers illustrative of theinvention are the following monothioethers: dioctyl thioether;octyldecyl thioether; octyldodecyl thioether; oc-

tyltetradecyl thioether; octylcetyl thioether;

didecyl thioether; decyldodecyl thioether; decyltetradecyl thioether;decylcetyl thioether; didodecyl thioether; dodecyltetradecyl thioether;dodecylcetyl thioether; ditetradecyl thioether; tetradecylcetylthioether; dicetyl thioether; and dioctadecyl thioether. One quiteeffective type of diallwl monothioether is characterized by one longchain and one short chain; for example: dodecyl methyl monothioether,dodecyl ethyl monothioether, dodecyl propyl monothioether; tetradecylmethyl monothioether, tetradecyl ethyl monothioether, tetradecyl propylmonothioether; cetyl methyl monothioether, cetyl ethyl monothioether,and cetyl propyl monothioether.

Likewise, examples of dialkyl seleno ethers seleno ether,dodecyltetradecyl seleno ether,

dodecylcetyl seleno ether, ditetradecyl' seleno ether, tetradecylcetylseleno ether, dicetyl seleno ether, dioctadecyl selenoether; dodecylmethyl monoseleno ether, dodecyl ethyl monoseleno ether, dodecyl'propylmonoseleno ether; tetradecyl methyl monoselenoether, tetradecyl ethylmonoseleno ether, tetradecyl propyl monoseleno ether; ethyl monoselenoether, and cetyl propyl monoseleno ether.

The foregoing compounds are represented by the type formula- R-X-Riwhere R, and R1 may be the'same or different eral formulae:

R1 R-S(i )-o-R,

for example, monothioethane dialkyl diethers or dithioethan dialkyldiethers, are also effective in the combination of this invention. Theselatter compounds may be represented by the formulae:

iii-mi l and where R and R1 may be any of the alkyl radicals previouslylisted for these radicals, R2 and R: maybe either hydrogen or any one ofsuch alkyl radicals, and n may be any whole number. Sulfoxides suchasare not precluded.

It is to be understood that the invention in its broader aspects doesnot preclude the use of substituted alkyl radicals in the thioethercomponent of the composition. However, when such a substituent ispresent it should not be so close to the sulfur atom of the thioethergroup as to substantially destroy the essential thioethercharacteristics of the sulfur atom. Thus, functional groups in the alkylradicals of thioether which are positioned on the alkyl chain relativelyremote from the thioether sulfur atom may be utilized. For example,thioethers derived from oleic acid esters are effective compounds in thecetyl methyl monoseleno ether, cetyl- 15 combination of this invention.This type of compound may be represented by the formula:

where R, R1 and R1 are alkyl radicals, R1 preferably being a relativelyshort chain such as an ethyl group. The carbonyl group of the above typecompound is sufllciently'far removed from the thioether group as not tomask or adversely affect the action of the thioether structure.Likewise, the thioethers remain essentially dialkyl thioether, eventhough aryl or other nonaliphatlc radicals be attached to the alkylchain at a point remote from the thioether group, and such compounds maybe utilized in the combination herein disclosed.

The thioethers utilized herein may be prepared by methods known in theart. For example, a monohalogenated hydrocarbon may be reacted with amercaptide to yield a thioether according to the reaction- RC1+RiSNa-RSR1+NaCl dation or absorption of oxygen at superatmospherictemperatures.

Decreased deterioration of the type which causes corrosion of modernbear ing metals is additionally among the improvements. The dialkylthioethers or seleno ethers in general serve as a corrosion inhibitorand/or a sensitizer to enhance the responsiveness of the hydrocarbon oilto the stabilizing action of the metal salt stabilizer. When the baseoil being stabilized is of high viscosity index or over-refined, thethioether or seleno ether ingredient usually functions primarily as asensitizer. When the base oil is of low viscosity index or lowrefinement the ingredient may serve primarily as a corrosion inhibitor.In moderately refined or moderate viscosity index base oils the ether tpe of ingredient may serve both as a sensitizer and a corrosioninhibitor. The following data illustrate the foregoing features of theinvention:

In tests whose results are 'reported'below the oils referred towere'subiected to oxidator tests particularly described in the Journalof Industrial 8: Engineering Chemistry, vol. 28, page 26, 1936. Thesetests were carried out at 300 F. and 340 F., as indicated, whichconditions it may be noted are extremely severe. The results of thetests are reported in cubic centimeters of oxygen absorbed per grams ofthe respective oils.

The inhibition period shown in various iii-- rm: I

C .ox boo Ozidator tests [M Cc. oxygen/100 00. oil after- 3m 5 211m.411m. chi-a. Oil on 0.5 hr. 1hr. 2hr. 4hr. WM Highly "11W! mphthwlc oilm igm 1,000 oo- Highly refined naphthenic base oil+1% HM nil'iit'iiiitiiiitmhrtse5on J m $313 fi iilfggc ly; l0 dimer 1'thioether-l-l% calcium oot i potassium cetyl xan- Phosp 12 24 63 w h iififif li y" l'ooo 50 1 000 Highly refined naphthenic base oil+27 ilgggfi ,feit;o;i ieetyl thi0cther+l% calcium oety potassium cemmn,phosphate 70 1 m0 thate+l% dicetyi 15 sulfide 70 100 1.000 1.1,

White oil hoavy+ Mention has been made of acid esters or inorzinc N-pganic acids such as partially esterifled acids of 1 edithiocarbamete. 4565 75 wl l i te oil heavy+l% phosphorus, as useful in obtaining a novelcoop- 1:32 l i ag gfig gg l erative action or activating effect withthioethers. +1%dicetylsulfldea 7 1o 14 The novel cooperative action ofsuch acid esters t li i n yf $353: is illustrated by the following data:

onate 1,000 0.1

w iiiito i u h ov i i 'z, Test: 111

00 any 0' oorhomtoflaz, dice- Oxidator data tylsulflde 1,000 0.45

White oil heavy-i-l% dibenzyl dithiocar- 3 oxygen m bonate 1,000 0.163400 1:;

White oil heavy+l% Oil a ts; are; 1. 2h

8 08 1'. rs. soiiide---." 10 1,ooo 0.7

Frorn the foregoing "data it will be noted that in the white oil heavy,dicetyl sulfide alone has little or no effect as an oxidation inhibitorunder White oil White oil+l% cetylethyl thioether White oil+1% dicetylphosphoric acid.

Greater than 1,000 cc.

first 36 hr.

Greater than 1,000 cc.

ii at h th particular severe conditions encountered. W lgte l i1 %ce:iylphosph0ric ci 15 y e or. Yet a substantially greater inhibition ofoxida" White oil+l% monooetyl phosphoric acid. Greater than 1,000 cc.tion or a substantially longer inhibition period White OM47 momcet 1 hosho Mid first% were eflected by the combination of the carbon- +170cetyleghyl 125 I 290 ates, thiocarbonates, or carbamates with dicetylsulfide in the on than with either component An additional indication ofthe novel cooperaalone. Thus the metal salt component appears t tor f rth tmoether The tive action of the ethers of thi invention and 0 Serveas 9111 ac 1 0 e salts of organo-inorganic acids comprises the rewhiteoil heavy used as a base oil in these tests duction in corrosion of copper-lead and cad is a very highly refined mineral oil from which i r ubtaut u an t now 5 mium-silver bearing metal alloys at elevated temmajorproport on o s s y o peratures. Table IV exemplifies this result:hydrocarbon components have been removed by refinement. IV

The following data illustrate the novel cooperatlve action betweenthioethers and salts of 300 F.0orrosion I test acids of phosphoruscontaining an organic substituent:

Oil Loss Loss TABLE II Cu-Pb Cd-Ag mg. mg. Oxidator data weight weight72 hrs. 72 hrs. i

Co. oxygeh absorbed I White 0 58 K; at 300 F. White oil+l calcium cetylghosphate. 128 147 Oil White oll+1 o eetylethyl sul de 41 0.4

i White oil+1% cetylethyl sulflde+1% calcium 2hrs. 4hrs. ohrs. cetylphosphate 25 2.9

' m White oil+l% calcium sulionates (from mineral oil) 53.2 82.8 Whiteoil Greater than ,000 cc. White oil+1% calcium sulfonates (from minflrsthr. eral oil)+l% dlcetyl sulfide i 26. 9 1.0 White oil+l% cetylethylthioether Greater than 1,000 cc. White oil+1% potassium cety 37. 2 32. 3

first M hr. White oil+l% potassium cetyl xanthate+l% 1. Write 0i1+l%calcium oetyl phosphate.-. Gr egteigan 1,000 cc. dicetylsulflde 19.0 0.4White oil+l% calcium cetyl phosphate o5 +0.25% cetylethyl thioether 5069 88 l Gum on stri white 0il+l% diOCtYl thi GfllGl'. 360 1 Stripdarkened,

White 0il;i-1l%hdi0c!l;y% thioether+1% cal- 40 (211111109 p 051) 8 9 l ls w vgi o 031522; cetyllmitlllifiltiilhioiglhei 7" 650 fir t h The termover-refined oil" is used to designate iteo' oety me y ioe er calcium gphosphate w 15 those oils from which naturally occurring inhibi T t H wI tors gormally priesent in the oil have been remove at least 0 anextent which materially White oil-+27 dioctadecyi throether. 2, 400wclgltq il-l-zy 'gld t g 1mi th +1% 107 168 p 257 reduces the stabilitof the oil against deteriorciumcey DOS!) 88 white on +1% ethanedimoethe, 360 ation t higher te p atures or w ich substan White oil+1%ethane dioctyldithloether tially increases corroslveness the oil on mod-+l% calcium cetyl phosphate 45 em bearing metals. Over-refined oils arenot r r. 7 Greater than 1,000 cc.

necessarily high viscosity index oils since oils of intermediateviscosity index are sometimes produced from quite low viscosity indexstocks by a severe refinement which causes a substantial reduction inthe natural inhibitor content of the oil and thereby produces an oilhaving a, correspondingly reduced stability. From the above it should beapparent that over-refined oils are not limited to thos produced bysolvent extraction. Other refining processes, e. g. sulfuric acidtreatment to produce white oils, remove naturallyoccurring inhibitorsoriginally in the oil when the treatment issufiiciently severe andthereby produce over-refinement with the attendant difficulties hereindiscussed.

In general, over-refined oils may be characterized as having naturalinhibitors removed to the point where the corrosiveness of the oil isgreater than about 40 mgs. on a 1" x 2" coarse grained copper-leadbearing in a 72-hour corrosion test (described below) run under thefollowing conditions:

Air rate m 30 liters per hour Temperature 300 F. Catalyst gms. of steelwool and 8 x t ip different types of the bearing metals were placed inthe oil. recorded. washed in petroleum ether and carefully wiped with asoft cotton cloth. The duration of the tests was 72 hours.

Highly solvent refined oils and other over-re- The weight loss of eachstrip was fined oils are not the only type which become definitelycorrosive to the newer bearing metals under normal but severe conditionsof use in internal combustion engines. It has been found that acorresponding adverse reaction, namely, corrosion'of alloy bearingmetals such as cadmium silver alloys, also occurs in parafiinicbase oilswhich have not been solvent refined or overrefined. The higher theviscosity index of the lubricating. oil the more pronoimced is thetendencY to corrosion of the kind referred to. Genthe ether givesmeasurable improvement, al-

though from approximately 0.1% to 2% is pre-' ferredwhere the compoundedoil is to be used as a crankcase lubricant for internal combustionengines. 5% or more by weight of the ethers may be dissolved in mineraloil or other suitable organic solvents for the purp se of preparing aconcentrate capable of dilution withlubricating oils and the like toyield a finished lubricant. Concentrates containing high percentages, e.g. 50% of the thioether and the salt of organo Before weighing, eachstrip was inorganic acid, comprise a convenient method of handling theseingredients and may be used as addition agents for lubricants in generalas well as for other purposes.

s g The preferred hydrocarbon oil is a mineral lubricating oil fractionsuch as a moderately acid refined naphthenic base lubricating oil. Otherbase oil stocks for the compounded oils involved herein may be utilizedsuch as the over-refined oils, solvent refined oils, parafiinic oilswith or without solvent refining. or highly refined naphthenic oils, aswell as synthetic hydrocarbon oils.

It is to be understood that the broader aspects of the invention are notlimited to any particular base stock since advantageous properties maybe obtained at least to some degree with various oils, the selection ofwhich will be determined by conditions and services which the Product isto encounter and by the particular combination of 20 additives utilized.

' The combination of comp unding agents hereinbefore disclosed may beadvantageously utilized in conJunction with metal salts of organic acidsin hydrocarbon oils.. Themetal salts of orgamc acids and the hereinpreviously-described additives cooperate to give enhanced stabilizingaction and each type of additive, in some instances, inhibitsundesirable eifects of the other type of addition agent in thecombination.

Examples of metal salts of organic acids which may be incorporated inlubricating oils, together with the thioethers or seleno ethers and theoxides, sulfides and selenides heretofore described, are metal salts ofhigher fatty or allphatic acids, metal salts of naphthenic acids, metalsalts of oil-soluble substituted phenols, and metal salts of carboxylicacids containing an aryl substituent.

Among'the metal salts of higher fatty acids 40 may be mentioned:aluminum laurate, aluminum oleate, aluminum stearate, aluminumricinoleate; zinc laurate, zinc oleate, zinc stearate, zinc ricinoleate;tin laurate, tin oleate, tin stearate. tin. ricinoleate; magnesiumlaurate, magnesium .45 oleate, magnesium stearate, magnesiumricinoleate; calcium laurate, calcium oleate, calcium stearate, calciumricinoleate; chromium laurate,

chromium oleate, chromium stearate, chromium ricinoleate; bariumlaurate, barium oleate, barium stearate, and barium ricinoleate.

Examples of metal napthenates are: aluminum naphthenate. zinc'naphthenate, magnesium naphthenate, cobalt naphthenate, cadmiumnaphthenate, tin naphthenate and manganese 'naphthenate. The uaphthenicacid component of these salts may conveniently be obtained frompetroleum.

Metal phenates which may be mentioned comtype formula:

It I

in, which it, v, w, a: and y are selected from the group consisting ofhydrogen, alkyl aryl, alkaryl, aralkyl and cyclic nonbenzen'oidhydrocarbon radicals. Specific illustrations 0]! such phenates are thealuminum, zinc,tin, magnesium, calcium, chromium and barium as well asother polyvalent metal salts of cetyl phenol. The phenolic radical ofthe salts preferably contains more than about 76 ten carbon atoms andalso should preferably have Prise metal salts of a substituted phenol ofthe an alkyl substituent substituted in the benzene ring to which thehydroxyl group of the phenol is directly attached.

Examples of carboxylic acids containing an aryl substituent are: phenylstearic acid, naphthyl stearic acid, phenyl lauric acid, alpha benzalstearic acid, alpha benzal lauric acid, and analogous homologues ofthese acids formed by condensation of an aromatic aldehyde with a fattyacid according to the reactionwhere R1 is an alkyl and R2 an arylradical. Aluminum, zinc, tin, magnesium, calcium, chromium and barium,as well as other polyvalent metal salts of each of the above acids, maybe utilized.

The invention also includes salts of polycarboxylic acids. Examples ofsuch salts are the aluminum, zinc, tin, magnesium, calcium, chro- .miumand barium as well as other polyvalent metal salts of partiallyesterifled acids of the oxalic acid series, including oxalic aciditself, malonic acid, isosuccinic or methyl malonic acid and its alkylhomologues, as well as the corresponding salts of partially esterifledalkyl tartronic acid, partially esterifled malic acid and itshomologues, partially esterifled oxyglutaric acid, partially esterifledhydroxy adipic acid, partially esterifled tartaric acid, partiallyesterifled citric acid and the like.

The present invention is primarily concerned with improvement of liquidlubricating compositions, and the proportion of the foregoing metalsalts of organic acids shouldtherefore preferably be insufficient toform greases or cause substantial gelling oi the oil. In general, fromabout 0.1% to 2% by weight based on the finished oil may be utilized,and from approximately 0.5% to 1.5% by weight of the metal salts oforganic acids is preferred.

The addition agents of this invention may be utilized in hydrocarbonoils containing auxiliary compounding agents such as pour pointdepresrium, said ether being present in an amount willcient to stabilizesaid oil against deterioration under oxidizing conditions, and a salt ofan organo-inorganic acid in an amount sufiicient to enhance thestabilizing action of said ether.

2. A composition comprising a hydrocarbon oil, an ether of an element ofgroup VI-B ofMendelyeevs Periodic Table and selected from the classconsisting of sulfur, selenium and tellurium,

said ether being present in an amount sufficient to stabilize said oilagainst deterioration under oxidizing conditions, and a salt of anorganic substituted inorganic acid of a weak acid-forming element.

3. A composition comprising a hydrocarbon oil, a thioether in an amountsuflicient to stabilize said oil against deterioration under oxidizingconditions, and a salt of an organo-inorganic acid in an amountsuflicient to enhance the stabilizing action of said thioether.

4. A composition comprising a hydrocarbon oil containing a small amountof an ether of an element of group VIE-B of Me'nde-lyeevs Periodic Tableand selected from the class consisting of sulfur, selenium andtellurium, and a small amount of a compound of the type- (A) (X) (Z)(X1) (Rn) in which A represents a basic salt-forming substituent, X andx1 are selected from the group consisting of oxygen, sulfur andselenium, Z is an acid-forming element selected from groups II[A, IV,V-B and VI-B of Mendelyeev's Periodic Table, R is an organic radical,and n is a whole number no less than one.

5. A composition as defined in claim 4 wherein said ethe'r is a dialkylthioether.

6. A composition as defined in claim 4 wherein said ether is adialkyldithiodiether.

7. A composition comprising a hydrocarbon oil, an ether of an element ofgroup VI-B of Mendelyeevs Periodic Table of the Elements and selectedfrom the class consisting of sulfur, se-

lenium and tellurium, said ether being present sants, oiliness agents,extreme pressure addition in an amount sufllcient to stabilize said oilagents, blooming agents, compounds-for enhancing the viscosity index ofthe hydrocarbon oil and auxiliary stabilizing agents such as metalalcoholates. Further, thickening agents and/or metal soaps ingrease-forming proportions are not precluded from the broader aspects ofthe invention.

High molecular weight dialkyl seleno ethers andtelluro ethers disclosedherein and claimed in combination with salts of organo-inorganic acid 55in hydrocarbon oil are claimed broadly as addition agents forhydrocarbon oil and as new compositions of matter in our copendingapplications Serial Nos. 476,759 and 476,760, respectively, filedFebruary 22, 1943. a

. 00 While the character of the invention has been described in detailand numerous examples of the compounds given, this has been done by wayof illustration only and with the intention that no limitation should beimposed upon the invention thereby. It will be apparent to those skilled'Mendelyeevs Periodic Table and selected from against deteriorationunder oxidizing conditions, and a salt of an acid of boron containing anorganic suhstituent.

8. A composition comprising a hydrocarbon oil, an ether of an element ofgroup VI-B of Mendelyeevs Periodic Table of the Elements and selectedfrom the class consisting of sulfur, selenium and tellurium, said etherbeing present in an amount sufilcient to stabilize said oil againstdeterioration under oxidizing conditions, and a salt of an acid ofsulfur containing an organic suhstituent.

9. A composition comprising a hydrocarbon oil,-an ether of an element ofgroup VI--B of Mendelyeevs Periodic Table of the Elements and selectedfrom the class consisting of sulfur, selenium and tellurium, said etherbeing present in an amount suiflcient to stabilize said oil againstdeterioration under oxidizing conditions, and a salt of a partiallyesterifled carbonic acid.

10. A composition comprising a hydrocarbon oil, an ether of an elementof grounvI-B oi Mendelyeevs Periodic Table and selected from the classconsisting of sulfur, selenium and tellurium, said ether being presentin an amount .suflicient to stabilize said oil against deteriorationunder'oxidizing conditions, and a polyvalent metal salt of anorgano-inorganic acid in an amount sumcient to. enhance the stabiliztheclass consisting of suliur, selenium and tellu- 1| ins tion of saidethen 11. A composition comprising a hydrocarbon oil containing a smallamount of an ether of an element of group VI-B of Mendelyeevs PeriodicTable and selected from the class consisting of sulfur, selenium andtellurium, and a small amount of a compound of the type-- (A) (x) (z)(x1) (Rn) in which A represents a polyvalent metal saltformingsubstituent, x and X1 are selected from the group consisting of oxygen,sulfur and selenium, Z is an acid-forming element selected from groupsHIA, IV, VB and VI-B of Mandelyeevs Periodic Table, R is an organicradical, and n is a whole number no less than one.

12. A composition comprising a, hydrocarbon oil, an ether of an elementof group V'I-B of Mendelyeevs Periodic Table of the Elements andselected from the class consisting of sulfur, seleniumand tellurlum,said ether being present in an amount suficient to stabilize said oilagainst deterioration under oxidizing conditions, and a polyvalent metalsalt of an acid of boron containing an organic substituent.

13. A composition comprising a hydrocarbon oil, an ether of an elementof group VI--B of Mendelyeevs Periodic Table of the Elements andselected from the class consisting of sulfur, selenium and tellurium,said ether being present in an amount suflicient to stabilize said oilagainst deterioration under oxidizing conditions, and a polyvalent metalsalt of a partially esterified carbonic acid.

14. An addition agent capable of inhibiting deten'oration of hydrocarbonoils under oxidizing conditions, comprising a concentrated solution inhydrocarbon oil of an ether of an element of group VI-B of MendelyeevsPeriodic Table of the Elements and selected from the class consisting ofsulfur, selenium and tellurium, and a polyvalentv metal salt of anorgano-inorganic acid, said solution being capable of dilution withmineral lubricating oil to form a homogeneous mixture containing fromapproximately 0.05% to 2% by weight based on the oil of said ether, andfrom approximately 0.05% to 2% by weight of said salt.

GEORGE H. DENISON, JR. PAUL C. CONDIT.

